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WO1980002671A1 - Traitement de polymeres - Google Patents

Traitement de polymeres Download PDF

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Publication number
WO1980002671A1
WO1980002671A1 PCT/GB1980/000099 GB8000099W WO8002671A1 WO 1980002671 A1 WO1980002671 A1 WO 1980002671A1 GB 8000099 W GB8000099 W GB 8000099W WO 8002671 A1 WO8002671 A1 WO 8002671A1
Authority
WO
WIPO (PCT)
Prior art keywords
die
polymer
process according
workpiece
gpa
Prior art date
Application number
PCT/GB1980/000099
Other languages
English (en)
Inventor
I Ward
A Gibson
P Coates
Original Assignee
Nat Res Dev
I Ward
A Gibson
P Coates
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nat Res Dev, I Ward, A Gibson, P Coates filed Critical Nat Res Dev
Priority to DE8080900985T priority Critical patent/DE3069144D1/de
Publication of WO1980002671A1 publication Critical patent/WO1980002671A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/30—Drawing through a die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2059/00—Use of polyacetals, e.g. POM, i.e. polyoxymethylene or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2061/00—Use of condensation polymers of aldehydes or ketones or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • B29L2023/22—Tubes or pipes, i.e. rigid

Definitions

  • U.K. Patent No. 1311885 discloses a process for reducing the cross-sectional area of an article of an orientable, theremoplastic polymeric material by drawing the article, at a temperature below its melting point, through a well-lubricated die of smaller cross-sectional area than that of the article, which process comprises forming an integral, preferentially oriented nose at one end of the article by a solid phase deformation process, such that the tensile strength of the nose exceeds the draw tension to be applied to the article, gripping the nose and drawing the article through the die so as to induce a substantial degree of molecular orientation throughout the drawn article.
  • U.K. Patent No. 1480479 discloses a process for the production of an oriented polymer material which comprises preparing a polymeric workpiece by cooling a semi-crystalline polymer having a natural draw ratio greater than 6 from the melt at a rate from 0.1 to 10oC per minute thereby obtaining the workpiece with substantially uniform morphology in cross-section; and deforming the workpiece below the melting point of the polymer by application of pressure.
  • a process for the solid phase deformation of a workpiece of an orientable thermoplastic polymer comprises: providing the workpiece of the essentially unoriented polymer at the entry side of a die; applying to the workpiece from the exit side of a die a draw tension insufficient to cause tensile failure of the workpiece; and drawing the workpiece through the die so that its plastic strain is progressively increased during start-up of the process.
  • workpiece includes bars, strips, rods, multifilaments, tubes and other cross-sections of solid or hollow stock.
  • the term includes both billets and other forms of stock of greater length; indeed, continuous stock, which may be formed as the process is performed, may be utilised: examples include a polymer sheathed continuous core such as a metal wire, or continuous polymer rod, film or filaments.
  • the orientable thermoplastic polymer is desirably a semicrystalline polymer, especially one which exhibits sufficient strain hardening and strain rate dependence of the flow stress,to stabilise the neck formed under the desired drawing- conditions.
  • Preferred such polymers are unsubstituted or fluoro-substituted vinyl polymers and polyacetals, suitably a linear homo- or copolymer of ethylene or propylene with at least one comonomer, a vinylidene fluoride polymer or a homo- or co-polyoxymethylene.
  • a workpiece of a linear homo- or copolymer of ethylene should desirably comprise a polymer having a weight average molecular weight less than 1,000,000, suitably from 50,000 to 500,000, preferably from 70,000 to 400,000; one of a linear homo- or copolymer of propylene should desirably comprise a polymer having a from 150,000.to 800,000, preferably from 250,000 to 500,000.
  • the die drawing process of this invention may also be performed, to provide a more advantageous forming process but not the enhanced properties listed above, on a workpiece of an essentially unoriented but orientable, amorphous polymer or an essentially unoriented but orientable, semi-crystalline ultra high molecular weight polymer (for example, a linear homopolymer of ethylene having a about 3,000,000). It may likewise be utilised, but to a lower deformation ratio, in respect of those polymers which would otherwise give the enhanced properties listed above.
  • an essentially unoriented but orientable, amorphous polymer or an essentially unoriented but orientable, semi-crystalline ultra high molecular weight polymer for example, a linear homopolymer of ethylene having a about 3,000,000. It may likewise be utilised, but to a lower deformation ratio, in respect of those polymers which would otherwise give the enhanced properties listed above.
  • thermoplastic polymer workpieces used in the process of this invention may be filled.
  • useful fibrous fillers include glass, asbestos, metal, carbon and ceramic whiskers, such as those formed from silicon carbide.
  • useful laminar fillers include mica, talc and graphite flakes. Chalk and fly ash may also be included.
  • the amount of filler which may advantageously be included depends on the nature of the filler, but up to 50% by weight, preferably less than 30%, especially less than 20%, may be incorporated.
  • essentially unoriented means that the workpiece has incurred no orientation other than that minor amount which might be induced during formation of the workpiece, for example during billet moulding or melt extrusion, or during any subsequent shaping thereof, for example by machining, prior to the performance of the die drawing process of this invention.
  • the workpiece may be formed either in the batch or continuously. In either case, where the cross-sectional area of the workpiece is substantially greater than that, for example, of a; textile filament care must be taken to ensure that the workpiece cools sufficiently slowly to prevent voids and stress cracking from occurring.
  • the polymer may be melted in a screw extruder; extruded or injected into a billet mould at a temperature about 30oC above its melting point and cooled under elevated pressure for 5 hours, or it may be melted in an extruder; extruded or injected into a cold billet mould; transferred to an oven for 4 hours under ambient pressure at a temperature below its melting point but above its crystallisation temperature; and thereafter allowed to cool in the oven after the heating has been switched off.
  • the polymer may also be injection moulded into an air or water cooled billet mould.
  • the work-piece is to be hollow it may be formed in the batch by including a mandrel of appropriate cross-section, usually coaxially, in the mould. Alternatively stock of circular solid or hollow cross-section may be produced continuously using one of several processes known to those skilled in the art.
  • the plastic strain of the workpiece is progressively increased during start-up of the process.
  • This can be effected, in accordance with one embodiment of the invention, by utilising a workpiece wherein that end (herein termed the "nose") of the workpiece to which the draw tension is applied is of progressively reduced: ( either continuously or in stages ) cross section.
  • nose that end
  • the die drawing process of this invention is not, however, limited to such cross-sections
  • the first alternative may be effected either by fabricating the work-piece with a conical nose, for example, by machining the workpiece to form a conical nose, or moulding the billet with a conical nose.
  • the semi-angle of the nose should be less than that of the die through which the workpiece is to be drawn.
  • the second alternative may be effected by fabricating, for example by machining the workpiece so that it has at least one, and preferably a plurality, for example from 2 to 4, of stages of progressively reduced cross-section, which together form a nose as shown in Figure 3 of the accompanying drawing.
  • the plastic strain of the workpiece can be progressively increased by providing at the entry side of the die a workpiece of essentially uniform cross section and, during start-up of the process, progressively reducing the aperture of the die orifice. Both such embodiments may be effected simultaneously.
  • the nose is advanced to protrude through the die lips and is secured to tensioning means applied from the exit side of the die.
  • a suitable arrangement includes a hauloff comprising a pair of serrated jaws in which the nose is gripped; a high tensile cable one end of which cable is attached to the jaws, the other to a winch or a loading station to which a turning moment or mass may be applied thereby applying a draw tension to the nose.
  • the hauloff may also comprise, instead of a cable, any tension transmitting means used in the metal drawing art including a chain, a rack and pinion mechanism, a screw mechanism and a hydraulically operated draw mechanism.
  • the hauloff may further comprise a pair of continuous contra-rotating friction belts, generally known as a "caterpillar".
  • the draw tension should be sufficient to draw the workpiece through the die but insufficient to cause tensile failure of the article; that is, the draw tension should be such that the true stress at any point of the product does not exceed its fracture stress at that point.
  • a suitable maximum value of draw tension may readily be determined by routine experiment. In the case of strain hardening polymers, as the drawing progresses the flow stress of the strained portions of the workpiece increases. This will permit a greater draw tension to be applied (giving an increased plastic strain). This enables greater cross-sections of workpiece, or smaller apertures of die, 01 both, to be utilised also giving a further increase in plastic strain.
  • the die temperature (which will be only a nominal temperature for the polymer since the process is not an isothermal one) and the work-piece shape and vary, by experiment, the draw speed to obtain the desired deformation ratio.
  • the die temperature is desirably set within 60 C below the melting point of the polymer. More particularly, for such polymers of from
  • the die temperature is preferably from 70°C to
  • the die temperature may be set from 20 - 170oC, preferably 90° - 130°C.
  • a die temperature of 80° - 170°C, preferably 150° - 170°C is suitable for homo- or copblyoxymethylene and of 80oC to 165oC is suitable for vinylidene fluoride polymers.
  • the polymer temperature may be further controlled by utilising a die with a temperature controlled chamber which extends downstream. It is feasible to use draw speeds greater than 1 cm min -1 in the die drawing process of this invention; indeed, speeds of 50 cm min -1 or more are preferred.
  • hollow stock is being die drawn by the process of this invention it is essential to provide an appropriately dimensioned mandrel on the entry side of the die and protruding between the die lips, to prevent collapse.
  • this mandrel can suitably be of the "floating plug" type.
  • a fixed mandrel may be used.
  • a batch process may be converted to a continuous one by putting the upstream end of the deforming workpiece and the downstream end of stock of the same cross-section both in contact with a hot, stainless steel plate; removing the plate and welding the two polymer surfaces.
  • a weld should be at an angle of 45 or less to the axis of the stock.
  • Figure 1 represents an axial section of a coextrusion line in accordance with the invention
  • Figure 2 represents an axial section of an automated continuous extrusion line in accordance with the invention.
  • a polymer coating 1 is supplied as melt flow from an extruder fitted with a crosshead annular die 2 through the centre of which the member to be coated 3 (such as cable, wire, rod or tube) is allowed to pass.
  • the melt then passes through a cooling zone 4 where it is solidified.
  • the solidified coating 1 is essentially isotropic and is not in intimate contact with the surface of the member to be coated 3.
  • Both member and isotropic coating then pass into a drawing block 5 of similar design to that already described and are heated to the drawing temperature.
  • the polymer coating is next drawn through the converging die 6 mounted in the drawing block. Deformation of the polymer continues beyond the drawing block for some distance before it becomes "frozen-out".
  • both member and coating are travelling with the same velocity, and the coating is in intimate contact with the member.
  • the velocity of the process is controlled and determined by a haul-off "caterpillar" device 7 situated downstream from the final deformation zone.
  • the ratio of the cross-sectional area of the isotropic polymer tube entering the die block to that of the annular clearance between coated member and die bore is of great importance, as will be understood from the foregoing description of the process. This ratio is controlled and determined by the rate, of output of the melt extruder which supplies the crosshead die.
  • This embodiment of the invention can be used to coat several items simultaneously; used where the cross-section is not circular; or used where two or more different polymers are co-extruded.
  • a polymer billet 8 is continuously extruded through a die 9 as described in British patent application 15023/79. The billet is then advanced to a drawing block 10 and drawn by a haul-off device (not shown) through a converging die 11 mounted in the drawing block.
  • the haul-off velocity and the temperatures of the billet 8 and the drawn product 12 are continuously monitored; their values being input into a computer 13 whence output regulating the melt extrusion rate and quality given by the extruder 14 is provided to the hopper feed 15, the screw drive l6, the barrel heater 17 and the infinitely variable orifice controlled by butterfly valve 18.
  • homo- and copolymers of polypropylene which have been deformed by passage through a die in the solid phase having a Young's modulus greater than 18, suitably greater than 20, preferably greater than 23 GPa, especially greater than 25 GPa.
  • This invention further provides a homo or copolyoxymethylene which has been deformed by passage through a die in the solid phase and having a Young's modulus greater than 25 GPa, preferably greater than 27 GPa.
  • This invention further provides a vinylidene fluoride polymer which has been deformed by passage through a die in the solid phase and having a Young's modulus greater than 3 GPa, suitably greater than 5 GPa preferably greater than 8 GPa.
  • This invention also provides copolymers of linear polyethylene, particularly copolymers comprising a minor amount of hexene-1, especially those which have been deformed by passage through a die in the solid phase, having a Young's modulus greater than 30 GPa, preferably greater than 40 GPa. Such copolymer materials cannot be produced at high deformation ratios by conventional drawing or solid state extrusion.
  • This invention further provides a Portland cement or concrete mass incorporating fibres either prepared as such or by fibrillating a film prepared by the process of this invention, particularly fibres of an ethylene-hexene-1 copolymer. The advantages of the die drawing process of this invention over hydrostatic extrusion will be manifest to those skilled in the art.
  • a polypropylene block copolymer having weight average molecular weight of 650,000 (PROPATHENE GSE 108 ex I.C.I.) was melted at
  • the protruding nose of the billet formed by the first stage was gripped at the exit side of the die and the billet, at an initial temperature of 110oC, was drawn through the die at a speed of 10mm min at a tension of 32.5 kg wt until all of the second stage had been drawn.
  • the grip was then repositioned on part of the billet corresponding to the second stage and drawing recommenced, until sufficient of the third stage had been drawn through the die to enable the grip to be affixed thereto, at a draw speed of 10 mm min -1 at a tension of 92.5 kg wt.
  • the grip was finally positioned on the drawn part of the third stage and the remainder thereof was drawn through the die at a draw speed of 500mm min at a tension of 152 kg wt to give an oriented rod of actual deformation ratio 12.7 (average diameter
  • Example 1 was repeated using a high density polyethylene homopolymer of 312,000, 33,000 (H020-54P ex BP Chemicals).
  • the respective draw speeds. and tensions were 10mm min -1 at 22 kg wt; 10mm min -1 at 55 kg wt and 500mm min - 1 at 78 kg wt.
  • the oriented rod had an actual deformation ratio of 10 (average diameter 3.88mm) and a flexural Young's modulus of 14 GPa.
  • Example 1 was repeated using polyoxymethylene of 45,000 and Mw/Mn slightly greater than 2 (Delrin 500 ex Du Pont). The die had its temperature set at 160oC.
  • the oriented rod had an actual deformation ratio of 12.6 and a flexural Young's modulus of 20 GPa.
  • EXAMPLE 4 A high density polyethylene homopolymer of 135,000, 25,500 and melt flow index of 0.6 dg min -1 . (006-60 ex BP Chemicals) was injection moulded using a mould with a 10mm diameter cylindrical cavity. The barrel temperature was 190oC, and the mould temperature was 110 C. The mould was held under injection pressure for 10 minutes to allow cooling and solidification to take place.
  • the initial isotropic billet had a diameter of 7mm one end of which was machined to give an essentially conical nose of 5 semi-angle which was extended for 20mm as a rod of diameter 4mm for gripping purposes.
  • the machined billet was then advanced into a conical die of 15 semi-angle, a bore diameter of 4mm and a temperature set at 100°C.
  • the protruding nose of the billet was gripped at the exit side of the die and the billet, at an initial temperature of
  • the oriented material protruding from the. exit side of the die was then regripped and drawing was recommenced at 5mm min -1 .
  • a high density polyethylene homopolymer (H020-54P ex BP Chemicals) was compression moulded as follows: a two-part mould was filled with polymer powder, heated to 210oC and left for 20 minutes to attain thermal equilibrium. The mould was then placed between the platens of a press and the powder compressed into a cavity of dimensions 20mm ⁇ 20mm ⁇ 200mm. A force of 1200 KN was used. The platens were then water cooled and moulding pressure maintained until the mould temperature had fallen below 80°C.
  • the initial isotropic billet had a diameter of 12mm one end of which was machined to give an essentially conical nose of 5o semi-angle which was extended for 20mm as a rod of diameter 4mm for gripping purposes.
  • the machined billet was then advanced into a conical die of 15o semi-angle, a bore diameter of 4mm and a temperature set at 100°C.
  • the protruding nose of the billet was gripped at the exit side of the die and the billet, at an initial temperature of 100oC, was drawn through the die at an initial speed of 5mm min -1 .
  • the machined billet was then advanced into a conical die of 15° semi-angle, a bore diameter of 4mm and a temperature set at
  • the protruding nose of the billet was gripped at the exit side of the die and the billet, at an initial temperaturree cof 130oC, was drawn through the die at an initial speed of 5mm min -1 After 100mm of material had been drawn through the die the drawing was stopped and the product cut off 20mm from the die. The oriented material protruding from the exit side of the die was then regripped and drawing was recommenced. The load rose to 4 kg. The draw speed was then gradually increased to 200mm min -1 . The load rose to a steady state value of 20 kg.
  • a melt extruder was used to fill a cylindrical aluminium mould, which was then placed vertically in an oven to allow solidification of the polymer.
  • a temperature gradient was maintamed in the oven so that the bottom of the mould was at 110° and the top at 120oC. This procedure ensured that solidification of the polymer took place from the bottom of the mould upwards, preventing the formation of internal voids due to shrinkage.
  • the initial, isotropic billet had a diameter of 9mm one end of which was machined to give an essentially conical nose of semi-angle which was extended as a rod of diameter 4mm for gripping purposes.
  • the machined billet was then advanced into a conical die of 15 semi-angle, a bore diameter of 4mm and a temperature set at 100°C.
  • the protruding nose of the billet was gripped at the exit side of the die and the billet, at an initial temperature of
  • a high density polyethylene homopolymer (006-60 ex BP Chemicals) was injection moulded using a mould with a cylindrical cavity.
  • the barrel temperature was 190oC and the mould temperature was 110oC.
  • the mould was held under injection pressure for 10 minutes to allow solidification to take place.
  • the initial, isotropic tube billet was machined from the moulding.
  • the tube billet had an internal diameter of 2mm and an external diameter of 8mm.
  • An essentially conical nose of 5 semi-angle which was extended as a tube with an outer diameter of 4mm for gripping purposes was machined on one end of the billet surface.
  • the machined billet was then advanced into a conical die of 15 semi-angle, a bore diameter of 4mm and a temperature set at 100oC.
  • a fixed mandrel of 2mm diameter was then inserted into the billet.
  • the protruding nose of the billet was gripped at the exit side of the die and the billet, at an initial temperature of 100oC, was drawn through the die at an initial speed of 5mm min -1
  • After 100mm of material had been drawn through the die the drawing was stopped and the product cut off 20mm from the die.
  • the oriented material protruding from the exit side of the die was then regripped and drawing recommenced.
  • the load rose to 30 kg.
  • the draw speed was then progressively increased to a steady value of 50mm min -1 .
  • the load increased to a steady state value of 31 kg.
  • a polypropylene copolymer (PROPATHENE GSE 108 ex I.C.I.) was extrusion moulded into a tube billet mould.
  • Example 8 The procedure of Example 8 was then essentially repeated with the internal diameter of the tube billet 2mm, the external diameter 7.17mm.
  • the initial temperature of the polymer was 110oC and the steady state draw speed was 4 ⁇ mm min
  • EXAMPLE 10 Twenty-four filaments of a high density polyethylene homopolymer of 102,000, 6,200 (Rigidex 50 ex BP Chemicals) were melt spun into a glycerol bath at 118oC. The isotropic filaments had a diameter of 1.36mm. Each filament was necked by contact with a hot stainless steel plate and the necked tow was then inserted into a conical die of 15 semi-angle, a bore diameter of 4mm and a temperature set at 100oC.
  • the protruding tow was then gripped at the exit side of the die and, at an initial temperature of 100oC, was drawn through the die at a draw speed which was progressively increased to a steady state value of 100mm min -1 .
  • a polymer composite containing 75% polypropylene ("Propathene" ex I.C.I.) and 2.5% chopped glass fibres (by weight) was moulded into rod using a melt extrusion process.
  • the initial billet machined from the moulded rod had a diameter of 9.8mm, one end of which was machined to give an essentially conical nose of 5 semi-angle which was extended as a rod of 4mm diameter for gripping purposes.
  • the machined billet was then advanced into a conical die of 15 semi-angle, a bore diameter of 4mm and a temperature set at 110°C.
  • the protruding nose of the billet was gripped at the exit side of the die and the billet, at an initial temperature of 110oC, was drawn through the die at an initial speed of 5mm min -1 . After 100mm of material had been drawn through the die, the drawing was stopped and the product cut off 20mm from the die. The oriented material protruding from the exit side of the die was then regripped and drawing was recommenced. The load rose to 69 kg.
  • a polyvinylidene fluoride homopolymer of 171,000 (Solef XI0N, ex Solvay) was injection moulded using a mould with a 10mm diameter cylindrical cavity.
  • the barrel temperature was 220oC and the mould temperature was 20oC.
  • the mould was held under injection pressure for 5 minutes, during which time it was cooled by progressive immersion in a water bath. This procedure ensured that solidification of the polymer took place from the bottom of the mould upwards, preventing the formation of internal voids due to shrinkage.
  • the initial isotropic billet was machined to a diameter of 9.80mm, one end being further machined to give an essentially conical nose of 5 semi-angle, which was extended for 20mm as a rod of diameter 4mm for gripping purposes.
  • the machined billet was then advanced into a conical die of 15 semi-angle, a bore diameter of 4mm and at a temperature 140oC.
  • the protruding nose of the billet was gripped at the exit side of the die and the billet, at an initial temperature of 140oC, and was drawn through the die at a speed of 10mm min -1 .
  • the drawing was stopped and the product was cut off 20mm from the die.
  • the oriented material protruding from the exit side of the die was then regripped, and drawing was recommenced at 10mm min -1 .
  • the load rose to a value of 112 kg and remained constant thereafter.
  • the polyvinylidene fluoride has a number average molecular weight from 1.0 to 1.9 ⁇ 10 5 , preferably from 1.3 to
  • Such material may be die-drawn to deformation ratios in excess of 6, for example 6.5 to 8 or even more.
  • a high density polyethylene homopolymer of 67,800, 13,350 (140-60 ex BP Chemicals) was extrusion moulded into a cylindrical tube, which was then placed vertically in an oven to allow slow cooling solidification of the polymer.
  • An isotropic billet for die-drawing was machined to a diameter of 8.94 mm one end being a cone of 5 semi-angle which was extended as a rod of 4mm diameter for gripping purposes.
  • the machined billet was advanced into a conical die of 15 semi-angle and bore diameter of 4mm, set at a temperature of 110oC.
  • the protruding nose of the billet was gripped at the exit side of the die and the billet, at an initial temperature of 110oC, was drawn through the die at a preliminary draw speed of 5mm min -1
  • a copolymer of ethylene and hex-1-ene (002-55 ex BP Chemicals) was extrusion moulded in the following manner: A melt extruder was used to fill a cylindrical aluminium mould, which was then placed vertically in an oven at 120°C to allow solidification of the polymer.
  • the initial, isotropic billet had a diameter of 11.31mm and one end was machined to give a conical nose of 5 semi-angle which was extended as a rod of diameter 4mm for gripping purposes.
  • the machined billet was then advanced into a conical die of 15° semi-angle, a bore diameter of 4mm and a temperature set at 100°C.
  • the protruding nose of the billet was gripped at the exit side of the die and then the billet, at an initial temperature of

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Des plastiques thermodurcissables orientes ayant des proprietes ameliorees telles que le module d'Young, la resistance au fluage, la resistance au transport gazeux, sont prepares par etirage du materiau plastique dans la phase solide au travers d'une matrice de sorte que sa deformation plastique augmente progressivement pendant la mise en marche.
PCT/GB1980/000099 1979-06-06 1980-06-06 Traitement de polymeres WO1980002671A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE8080900985T DE3069144D1 (en) 1979-06-06 1980-06-06 Polymer processing

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB7919737 1979-06-06
GB7919737 1979-06-06
GB7941427 1979-11-30

Publications (1)

Publication Number Publication Date
WO1980002671A1 true WO1980002671A1 (fr) 1980-12-11

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ID=26271776

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1980/000099 WO1980002671A1 (fr) 1979-06-06 1980-06-06 Traitement de polymeres

Country Status (6)

Country Link
EP (1) EP0038798B1 (fr)
JP (1) JPH0149611B2 (fr)
AT (1) ATE9292T1 (fr)
DE (1) DE3069144D1 (fr)
GB (1) GB2060469B (fr)
WO (1) WO1980002671A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0133355A2 (fr) * 1983-07-29 1985-02-20 National Research Development Corporation Matière polyester orientée limpide
EP0157601A2 (fr) * 1984-03-30 1985-10-09 National Research Development Corporation Produits tubulaires
WO1990006842A1 (fr) * 1988-12-12 1990-06-28 Raychem Corporation Conducteur electrique revetu de terephtalate de polybutylene
EP0627589A1 (fr) * 1993-06-04 1994-12-07 SOLVAY (Société Anonyme) Tube en polyoléfine biorienté
WO1997041906A1 (fr) * 1996-05-03 1997-11-13 Baxter International Inc. Tubulure orientee a usage medical
US5741452A (en) * 1996-05-03 1998-04-21 Baxter International Inc. Orienting extrusion processes for medical tubing applications
US5954702A (en) * 1996-05-03 1999-09-21 Baxter International Inc. Interface geometry for adhesive bonds
US6036676A (en) * 1996-05-03 2000-03-14 Baxter International Inc. Surface modified polymeric material formulation
US6129876A (en) * 1996-05-03 2000-10-10 Baxter International Inc. Heat setting of medical tubings
US6187400B1 (en) 1996-05-03 2001-02-13 Baxter International Inc. Medical tubing and pump performance enhancement by ionizing radiation during sterilization
US6328716B1 (en) 1996-05-03 2001-12-11 Baxter International Inc. Method of using medical tubings in fluid administration sets
US6506333B1 (en) 1996-05-03 2003-01-14 Baxter International Inc. Method of surface modifying a medical tubing
WO2008057167A1 (fr) * 2006-11-10 2008-05-15 Dow Global Technologies Inc. Étirage à l'état solide d'une composition polymère chargée pour obtenir une valeur stable de la cavitation et de la densité

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JPS60101032A (ja) * 1983-11-08 1985-06-05 Toyobo Co Ltd 高強力高弾性率結晶性重合体延伸物の製造方法
JPS60138507A (ja) * 1983-12-27 1985-07-23 Toyobo Co Ltd ポリエチレン抗張力線
GB2157298B (en) * 1984-04-13 1987-11-18 Nat Res Dev Solid phase deformation process
GB8428878D0 (en) * 1984-11-15 1984-12-27 British Telecomm Telecommunications cable
WO1989000493A1 (fr) * 1987-07-10 1989-01-26 The Broken Hill Proprietary Company Limited Articles a base de polymere oriente
GB2207436B (en) * 1987-07-24 1991-07-24 Nat Research And Dev Corp The Solid phase deformation process
WO1990008877A1 (fr) * 1989-02-06 1990-08-09 The Broken Hill Proprietary Company Limited Boulon d'ancrage en materiau polymere oriente
US5414049A (en) 1993-06-01 1995-05-09 Howmedica Inc. Non-oxidizing polymeric medical implant
GB9522477D0 (en) * 1995-11-02 1996-01-03 Howmedica Method of improving the wear quality of ultra-high molecular weight polyethylene
GB9522478D0 (en) * 1995-11-02 1996-01-03 Howmedica Prosthetic bearing element and implant incorporating such an element
US8563623B2 (en) 1996-02-13 2013-10-22 The General Hospital Corporation Radiation melt treated ultra high molecular weight polyethylene prosthetic devices
US8865788B2 (en) 1996-02-13 2014-10-21 The General Hospital Corporation Radiation and melt treated ultra high molecular weight polyethylene prosthetic devices
EP2319546A1 (fr) 1996-07-09 2011-05-11 Orthopaedic Hospital Réticulation de polyéthylène pour une usure faible utilisant la radiation et les traitements thermiques
EP1178764B1 (fr) 1999-04-21 2006-05-31 Howmedica Osteonics Corp. Procede de preparation d'un dispositif medical prothetique en polyethylene selectivement reticule, et dispositif ainsi produit
US6372068B1 (en) 1999-09-21 2002-04-16 Roger S. Kincel Composite polymeric twist tie
US7011879B1 (en) 1999-09-21 2006-03-14 Johnston International Corp. Composite polymeric twist tie
ES2221627T3 (es) 1999-12-20 2005-01-01 Psa Composites, Llc Procedimiento para formar material compuesto y material compuesto obtenido mediante el mismo.
CA2429930C (fr) 2002-06-06 2008-10-14 Howmedica Osteonics Corp. Polyethylene sequence reticule
GB201003274D0 (en) 2010-02-26 2010-04-14 A Fax Ltd Methods of connecting

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GB953734A (fr) * 1960-06-21
US2291670A (en) * 1939-08-31 1942-08-04 Dow Chemical Co Method of coating wire and the like
US3275730A (en) * 1962-12-24 1966-09-27 Hercules Inc Method and apparatus for orienting an extruded polymeric wire coating
NL6612434A (fr) * 1966-09-02 1966-12-27
US4021521A (en) * 1974-07-31 1977-05-03 Basf Aktiengesellschaft Manufacture of work-hardened wires and profiles

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JPS4879277A (fr) * 1972-01-26 1973-10-24
JPS5065450A (fr) * 1973-10-15 1975-06-03
JPS54146866A (en) * 1978-05-10 1979-11-16 Hideo Watase Production of biaxially orientated synthetic resin pipe

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US2291670A (en) * 1939-08-31 1942-08-04 Dow Chemical Co Method of coating wire and the like
GB953734A (fr) * 1960-06-21
US3275730A (en) * 1962-12-24 1966-09-27 Hercules Inc Method and apparatus for orienting an extruded polymeric wire coating
NL6612434A (fr) * 1966-09-02 1966-12-27
US4021521A (en) * 1974-07-31 1977-05-03 Basf Aktiengesellschaft Manufacture of work-hardened wires and profiles

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0133355A2 (fr) * 1983-07-29 1985-02-20 National Research Development Corporation Matière polyester orientée limpide
EP0133355A3 (en) * 1983-07-29 1987-05-13 National Research Development Corporation Clear oriented polyester material
EP0157601A2 (fr) * 1984-03-30 1985-10-09 National Research Development Corporation Produits tubulaires
EP0157601A3 (en) * 1984-03-30 1987-06-03 National Research Development Corporation Tubular materials
WO1990006842A1 (fr) * 1988-12-12 1990-06-28 Raychem Corporation Conducteur electrique revetu de terephtalate de polybutylene
EP0627589A1 (fr) * 1993-06-04 1994-12-07 SOLVAY (Société Anonyme) Tube en polyoléfine biorienté
BE1007046A3 (fr) * 1993-06-04 1995-02-28 Solvay Tube en polyolefine bioriente.
US5741452A (en) * 1996-05-03 1998-04-21 Baxter International Inc. Orienting extrusion processes for medical tubing applications
WO1997041906A1 (fr) * 1996-05-03 1997-11-13 Baxter International Inc. Tubulure orientee a usage medical
US5932307A (en) * 1996-05-03 1999-08-03 Baxter International Inc. Oriented medical tubing
US5954702A (en) * 1996-05-03 1999-09-21 Baxter International Inc. Interface geometry for adhesive bonds
US6036676A (en) * 1996-05-03 2000-03-14 Baxter International Inc. Surface modified polymeric material formulation
US6129876A (en) * 1996-05-03 2000-10-10 Baxter International Inc. Heat setting of medical tubings
AU726109B2 (en) * 1996-05-03 2000-11-02 Baxter International Inc. Oriented medical tubing
US6187400B1 (en) 1996-05-03 2001-02-13 Baxter International Inc. Medical tubing and pump performance enhancement by ionizing radiation during sterilization
US6328716B1 (en) 1996-05-03 2001-12-11 Baxter International Inc. Method of using medical tubings in fluid administration sets
US6506333B1 (en) 1996-05-03 2003-01-14 Baxter International Inc. Method of surface modifying a medical tubing
WO2008057167A1 (fr) * 2006-11-10 2008-05-15 Dow Global Technologies Inc. Étirage à l'état solide d'une composition polymère chargée pour obtenir une valeur stable de la cavitation et de la densité
US8871130B2 (en) 2006-11-10 2014-10-28 Eovations, Llc Solid state drawing a filled polymer composition to a stable extent of cavitation and density

Also Published As

Publication number Publication date
DE3069144D1 (en) 1984-10-18
GB2060469B (en) 1983-09-28
ATE9292T1 (de) 1984-09-15
GB2060469A (en) 1981-05-07
JPS56500606A (fr) 1981-05-07
EP0038798B1 (fr) 1984-09-12
JPH0149611B2 (fr) 1989-10-25
EP0038798A1 (fr) 1981-11-04

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